Methods for forming a polycrystalline molybdenum film over a surface of a substrate and related structures including a polycrystalline molybdenum film

ABSTRACT

Methods for forming a polycrystalline molybdenum film over a surface of a substrate are disclosed. The methods may include: providing a substrate into a reaction chamber; depositing a nucleation film directly on an exposed surface of the substrate, wherein the nucleation film comprises one of a metal oxide nucleation film or a metal nitride nucleation film; and depositing a polycrystalline molybdenum film directly on the nucleation film; wherein the polycrystalline molybdenum film comprises a plurality of molybdenum crystallites having an average crystallite size of less than 80 Å. Structures including a polycrystalline molybdenum film disposed over a surface of a substrate with an intermediate nucleation film are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This Application is a nonprovisional of, and claims priority to and thebenefit of, U.S. Provisional Patent Application No. 62/891,247, filed onAug. 23, 2019 and entitled “METHODS FOR FORMING A POLYCRYSTALLINEMOLYBDENUM FILM OVER A SURFACE OF A SUBSTRATE AND RELATED STRUCTURESINCLUDING A POLYCRYSTALLINE MOLYBDENUM FILM,” and U.S. ProvisionalPatent Application No. 62/891,254, filed on Aug. 23, 2019 and entitled“METHODS FOR DEPOSITING A MOLYBDENUM NITRIDE FILM ON A SURFACE OF ASUBSTRATE BY A CYCLICAL DEPOSITION PROCESS AND RELATED SEMICONDUCTORDEVICE STRUCTURES INCLUDING A MOLYBDENUM NITRIDE FILM,” both of whichare hereby incorporated by reference herein.

FIELD OF INVENTION

The present disclosure relates generally to methods for forming apolycrystalline molybdenum film over a surface of a substrate andparticular methods for depositing a nucleation film directly on asurface of a substrate and subsequently depositing a polycrystallinemolybdenum film directly on the nucleation film. The present disclosurealso general relates to structures including a polycrystallinemolybdenum film disposed directly on a nucleation film.

BACKGROUND OF THE DISCLOSURE

Semiconductor device fabrication processes in advanced technology nodesgenerally require state of the art deposition processes for formingmetal films, such as, polycrystalline molybdenum films, for example.

A common requisite for the deposition of a metal film is that thedeposition process is extremely conformal. For example, conformaldeposition is often required in order to uniformly deposit a metal filmover three-dimensional structures including high aspect ratio non-planarfeatures. Another common requirement for the deposition of metal filmsis that the deposition process is capable of depositing ultra-thin filmswhich are continuous over a large substrate area. In the particular casewherein the metal film is electrically conductive, the depositionprocess may need to be optimized to produce low electrical resistivityfilms. For example, low electrical resistivity metal films commonlyutilized in state of the art semiconductor device applications mayinclude tungsten and/or copper. However, tungsten films and copper filmscommonly require a thick barrier layer, disposed between the metal filmand a dielectric material. The thick barrier layer may be utilized toprevent diffusion of metal species into the underlying dielectricmaterial thereby improving device reliability and device yield. However,the thick barrier layer commonly exhibits a high electrical resistivityand therefore results in an increase in the overall electricalresistivity of the semiconductor device structure.

Potential replacements for tungsten and copper films in next-generationdevices may include molybdenum films. For example, molybdenum (Mo) is alow electrical resistivity refractory metal that can potentially replacetungsten as a material in memory, logic, and other devices usingpolysilicon-metal gate electrode structures. A molybdenum film can alsobe used in some organic light emitting diodes, liquid crystal displays,and also in thin film solar cells and photovoltaics.

In addition, in particular semiconductor fabrication processes, it maybe desirable to form a metal film, such as, for example, apolycrystalline molybdenum film, within non-planar features (e.g.,vertical and/or horizontal trenches) disposed in/on a substrate. Theformation of a metal film within non-planar features may at leastpartially or fully fill the non-planar features with the metal film, aprocess commonly referred to as “gap-fill”. As semiconductor devicestructure geometries have decreased and high aspect ratio non-planarfeatures have become more common place in device structures such asDRAM, 3D-NAND, flash memory, and logic, it has become increasinglydifficult to fill non-planar features with a metal film having thedesired characteristics.

Accordingly, methods and related structures are desired for forming apolycrystalline molybdenum film with low electrical resistivity andphysical properties that enable a polycrystalline molybdenum gap-fillprocess on a substrate including non-planar features.

SUMMARY OF THE DISCLOSURE

This summary is provided to introduce a selection of concepts in asimplified form. These concepts are described in further detail in thedetailed description of example embodiments of the disclosure below.This summary is not intended to identify key features or essentialfeatures of the claimed subject matter, nor is it intended to be used tolimit the scope of the claimed subject matter.

In some embodiments, methods for forming a polycrystalline molybdenumfilm over a surface of a substrate are provided. The methods maycomprise: providing a substrate into a reaction chamber; depositing anucleation film directly on an exposed surface of the substrate, whereinthe nucleation film comprises one of a metal oxide nucleation film or ametal nitride nucleation film; and depositing a polycrystallinemolybdenum film directly on the nucleation film, wherein thepolycrystalline molybdenum film comprises a plurality of molybdenumcrystallites having an average crystallite size of less than 80 Å.

In some embodiments, structures including a polycrystalline molybdenumfilm are provided. The structures may comprise: a surface of asubstrate; a nucleation film disposed directly on the surface of thesubstrate, wherein the nucleation film comprises at least one of a metaloxide nucleation film or a metal nitride nucleation film; and apolycrystalline molybdenum film disposed directly on the nucleationfilm; wherein the polycrystalline molybdenum film comprises a pluralityof molybdenum crystallites having an average crystallite size of lessthan 80 Å.

For purposes of summarizing the invention and the advantages achievedover the prior art, certain objects and advantages of the invention havebeen described herein above. Of course, it is to be understood that notnecessarily all such objects or advantages may be achieved in accordancewith any particular embodiment of the invention. Thus, for example,those skilled in the art will recognize that the invention may beembodied or carried out in a manner that achieves or optimizes oneadvantage or group of advantages as taught or suggested herein withoutnecessarily achieving other objects or advantages as may be taught orsuggested herein.

All of these embodiments are intended to be within the scope of theinvention herein disclosed. These and other embodiments will becomereadily apparent to those skilled in the art from the following detaileddescription of certain embodiments having reference to the attachedfigures, the invention not being limited to any particular embodiment(s)disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

While the specification concludes with claims particularly pointing outand distinctly claiming what are regarded as embodiments of theinvention, the advantages of embodiments of the disclosure may be morereadily ascertained from the description of certain examples of theembodiments of the disclosure when read in conjunction with theaccompanying drawings, in which:

FIG. 1A illustrates a simplified cross-sectional schematic diagram of aprior art structure which includes a number of vertical trenches;

FIG. 1B illustrates a simplified cross-sectional schematic diagram ofthe prior art structure of FIG. 1A following the formation of a gap-fillfilm within the vertical trenches;

FIG. 2 illustrates an exemplary process flow, demonstrating a method forforming a polycrystalline molybdenum film over a surface of a substrateaccording to the embodiments of the disclosure;

FIG. 3 illustrates an exemplary process flow, demonstrating a firstcyclical deposition process for depositing a nucleation film directly onan exposed surface of a substrate according to the embodiments of thedisclosure;

FIG. 4 illustrates an exemplary process flow, demonstrating a secondcyclical deposition process for depositing a polycrystalline molybdenumfilm directly on a nucleation film according to the embodiments of thedisclosure;

FIG. 5A illustrates a simplified cross-sectional schematic diagram of astructure including a substrate with a number of non-planar features;

FIG. 5B illustrates a simplified cross-sectional schematic diagram ofthe structure of FIG. 5A following the deposition of a nucleation filmdirectly on an exposed surface of the substrate according to theembodiments of the disclosure; and

FIG. 5C illustrates a simplified cross-sectional schematic diagram ofthe structure of FIG. 5B following the deposition of a polycrystallinemolybdenum film directly on the nucleation film according to theembodiments of the disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it willbe understood by those in the art that the invention extends beyond thespecifically disclosed embodiments and/or uses of the invention andobvious modifications and equivalents thereof. Thus, it is intended thatthe scope of the invention disclosed should not be limited by theparticular disclosed embodiments described below.

The illustrations presented herein are not meant to be actual views ofany particular material, structure, or device, but are merely idealizedrepresentations that are used to describe embodiments of the disclosure.

As used herein, the term “substrate” may refer to any underlyingmaterial or materials that may be used, or upon which, a structure, adevice, a circuit, or a film may be formed.

As used herein, the term “cyclical deposition” may refer to thesequential introduction of two or more precursors (reactants) into areaction chamber to deposit a film over a substrate and includesdeposition techniques such as atomic layer deposition and cyclicalchemical vapor deposition.

As used herein, the term “cyclical chemical vapor deposition” may referto any process wherein a substrate is sequentially exposed to two ormore volatile precursors, which react and/or decompose on a substrate todeposit a desired film.

As used herein, the term “atomic layer deposition” (ALD) may refer to avapor deposition process in which deposition cycles, preferably aplurality of consecutive deposition cycles, are conducted in a reactionchamber. Typically, during each deposition cycle the precursor ischemisorbed to a deposition surface (e.g., a substrate surface or apreviously deposited underlying surface such as material from a previousALD deposition cycle), forming a monolayer or sub-monolayer that doesnot readily react with additional precursor (i.e., a self-limitingreaction). Thereafter, if necessary, a reactant (e.g., another precursoror reaction gas) may subsequently be introduced into the reactionchamber for use in converting the chemisorbed precursor to the desiredmaterial on the deposition surface. Typically, this reactant is capableof further reaction with the precursor. Further, purging steps may alsobe utilized during each deposition cycle to remove excess precursor fromthe reaction chamber and/or remove excess reactant and/or reactionbyproducts from the reaction chamber after conversion of the chemisorbedprecursor. Further, the term “atomic layer deposition,” as used herein,is also meant to include processes designated by related terms such as,“chemical vapor atomic layer deposition”, “atomic layer epitaxy” (ALE),molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, andchemical beam epitaxy when performed with alternating pulses ofprecursor composition(s), reactive gas, and purge (e.g., inert carrier)gas.

As used herein, the term “film” may refer to any physical continuous orphysically discontinuous structures and materials formed or deposited bythe methods disclosed herein. For example, “film” could include 2Dmaterials, nanolaminates, nanorods, nanotubes, nanoparticles, partial orfull molecular layers, partial or full atomic layers, or clusters ofatoms and/or molecules. “Film” may also comprise a material or a layerwith pinholes, but still be at least partially continuous.

As used herein, the term “molybdenum halide precursor” may refer to areactant which comprises at least a molybdenum component and a halidecomponent, wherein the halide component may include one or more of achlorine component, an iodine component, or a bromine component.

As used herein, the term “molybdenum oxyhalide” may refer to a reactantwhich comprises at least a molybdenum component, an oxygen component,and a halide component.

As used herein, the term “reducing agent” may refer to a reactant thatdonates an electron to another species in a redox chemical reaction.

As used herein, the term “polycrystalline film” may refer to a filmwhich displays at least short range ordering of the crystallinestructure of the film and also includes the terms “multicrystallinefilm”, or “polycrystal film”. “Polycrystalline film” also may refer to afilm comprising a plurality of crystallites.

As used herein, the terms “amorphous” and “amorphous film” may refer toa film which displays substantially no ordering of the structure of thefilm

As used herein, the term “crystallite size” may refer to average size ofa plurality of crystallites within a polycrystalline film as determinedby x-ray diffraction (XRD) measurements of the polycrystalline film.

As used herein, the term “non-planar feature” may refer to an opening orcavity disposed between two opposing surfaces of a non-planar substrateand may include “vertical non-planar features” and “horizontalnon-planar features”.

As used herein, the term “vertical non-planar feature” may comprise: anopening or cavity disposed between opposing inclined sidewalls of twoprotrusions extending upwards from a surface of a substrate, or opposinginclined sidewalls of an indentation extending downward into a surfaceof a substrate. Non-limiting examples of “vertical non-planar features”may include, but is not limited to: v-shaped vertical trenches, taperedvertical trenches, re-entrant vertical trenches, vertical openings,vertical voids, and vertical through-silicon-via trenches. For example,a vertical non-planar feature may comprise adjacent sidewalls which meetat a point at the base of the feature, or a vertical non-planar featuremay comprise a base of the feature that plateaus to a flat base surface.“Vertical” as used herein does not limit the slope of opposing sidewallsspecifically to a perpendicular incline with the horizontal plane of thesubstrate.

As used herein, the term “horizontal non-planar feature” may comprise:an opening or cavity disposed between two opposing substantiallyhorizontal surfaces, the opposing substantially horizontal surfacesbounding the “horizontal non-planar feature”.

As used herein, the term “line bending” may refer to a bending or adistortion of the regions of the substrate disposed between adjacentnon-planar features, the bending or distortion resulting from theformation of a gap-fill film within the non-planar features. Forexample, a non-planar substrate may comprise a plurality of “verticalnon-planar features” such as, vertical trenches, extending downward intothe substrate. The regions between adjacent “vertical non-planarfeatures” may be referred as line features. The line features mayundergo a line bending (i.e., a distortion) upon the formation of agap-fill metal within a substrate including a plurality of non-planarfeatures.

The concept of “line bending” is illustrated in greater detail withreference to FIGS. 1A-B which illustrate prior art methods for forming agap-fill film within a plurality of non-planar features.

In more detail, FIG. 1A illustrates a simplified cross-sectionalschematic diagram of a structure 100 prior to a gap-fill process. Thestructure 100 includes a substrate 102 including an array of non-planarfeatures 104, which in this example comprise vertical trenches disposedwithin the substrate 102. Disposed between each of the adjacent verticaltrenches 104 is a plurality of line feature 106. The plurality of linefeatures 106 may have a substantially regular pitch (x), wherein thepitch (x) may be defined as the distance between the middle verticalaxis of one line feature (e.g., axis 108A) to the middle vertical axisof an adjacent line feature (e.g., axis 108B). The array of verticaltrenches 104 as illustrated in FIG. 1A may comprise sloped sidewalls,wherein the width of each vertical trench decreases from the top/openingof a vertical trench down to the base of the vertical trench. The width(y) of each of the array of vertical trenches may be determined bymeasurement of the distance between opposing sidewalls of the verticaltrench. For example, in the structure 100 of FIG. 1A the verticaltrenches comprise v-shaped vertical trenches wherein the width (y) ofeach the v-shaped trenches may be determined by measuring the distancebetween the uppermost extent of opposing sidewalls, as illustrated inFIG. 1A.

As a non-limiting example, the structure 100 of FIG. 1A may comprise aportion of a partially fabricated dynamic random-access memory (DRAM)device structure prior to the deposition of a gap-fill film, wherein thepartially fabricated DRAM device structures includes a regular array ofburied wordline (bWL) trenches (e.g., vertical trenches 104), and DRAMwordlines (e.g., line features 106).

FIG. 1B illustrates a simplified cross-sectional schematic diagram of aprior art structure 110 which comprises the structure 100 (of FIG. 1A)following the deposition of a gap-fill film within the array of verticaltrenches, thereby filling the vertical trenches with the gap-fill film.As illustrated in FIG. 1B, the line features 106 disposed betweenadjacent vertical trenches 104 are bent (or distorted) due to thedeposition of the gap-fill film 112 and the once regular array of linefeatures 106 are more disordered due to the gap-fill film deposition.The bending of the line features 106 results in an increased variationof the width of the vertical non-planar structures 104 as denoted bywidth (z), e.g., as measured at the uppermost extent of the v-shapedvertical trenches of FIG. 1B.

As used herein, the term “percentage line bending” may quantify thedegree of line bending caused by the deposition of a gap-fill film on asubstrate including a regular array of non-planar features and linefeatures. The percentage line bending may be calculated by the followingequation (I):

$\begin{matrix}{{{percentage}\mspace{14mu} (\%)\mspace{14mu} {line}\mspace{14mu} {bending}} = {( \frac{offset}{pitch} ) \times 100}} & (I)\end{matrix}$

wherein the offset is calculated by the following equation (II):

offset=|

z

−

y

|  (II)

or in other words, the value of the offset equals the absolute value ofthe average width of the non-planar features (e.g., vertical trenches)pre gap-fill film deposition (average value of (z)), minus the averagewidth of the non-planar features (e.g., vertical trenches) pre gap-fillfilm deposition (average value (y)). As a non-limiting example, theoffset may be statistically established by measuring the width (y) of aplurality of non-planar features prior to gap-fill film deposition andsubsequently measuring the width (z) for a plurality of non-planarfeatures following the deposition of a gap-fill film in the non-planarfeatures. The average of (z) and the average of (y) may be determineutilizing high magnification microscopy techniques, such as, scanningelectron microscope, for example.

As used herein, the term “seam” may refer to a line or one or more macrovoids formed by the abutment of the leading edges of the gap-fill film.For example, a seam may refer to a region in a metal gap-fill filmwherein the leading edges of two metal films growing on opposingsidewalls of a non-planar feature touch each other. Therefore the “seam”is generally disposed at the center of a metal filled non-planarfeature. The formation of a seam in a metal gap-fill film may beundesirable and may result in poor device performance and subsequentissues in device fabrication. The presence of a “seam” within a gap-fillfilm may be observable using scanning transmission electron microscopy(STEM), or transmission electron microscopy (TEM).

A number of example materials are given throughout the embodiments ofthe current disclosure, it should be noted that the chemical formulasgiven for each of the example materials should not be construed aslimiting and that the exemplary materials given should not be limited bya given example stoichiometry.

The present disclosure includes methods for forming a polycrystallinemolybdenum film over a surface of a substrate utilizing an intermediatenucleation. Polycrystalline molybdenum films may be utilized in a numberof applications, such as, for example, low electrical resistivity metalgap-fill films, liner layers for 3D-NAND, DRAM word-line features, or asan interconnect material in CMOS logic applications. The ability todeposit a polycrystalline molybdenum film over a surface of a substrateutilizing an intermediate nucleation film, i.e., without the use of ahigh electrical resistivity liner layer, may allow for a lowerelectrical resistivity for interconnects in logic applications, i.e.,CMOS structures, and word-line/bit-line in memory applications, such as3D-NAND and DRAM structures.

In addition, the embodiments of the disclosure may provide nucleationfilms utilized for the deposition of polycrystalline molybdenum films,wherein the nucleation films may improve the quality of thepolycrystalline molybdenum films. For example, the deposition of thenucleation films prior to the deposition of the polycrystallinemolybdenum film may result in a polycrystalline molybdenum film with areduced surface roughness and/or a reduced crystallite size. Theimproved characteristics of the polycrystalline molybdenum films formedaccording to the embodiments of the disclosure may result in improved ametal gap-fill film and a reduction in the percentage line bending instructures including an array of non-planar features and line features.

Therefore, the embodiments of the disclosure may include methods forforming a polycrystalline molybdenum film over a surface of a substrateutilizing an intermediate nucleation film. The methods of the disclosuremay comprise: providing a substrate into a reaction chamber; depositinga nucleation film directly on an exposed surface of the substrate,wherein the nucleation film comprises one of a metal oxide nucleationfilm or a metal nitride nucleation film; and depositing apolycrystalline molybdenum film directly on the nucleation film, whereinthe polycrystalline molybdenum film comprises a plurality of molybdenumcrystallites having an average crystallite size of less than 80 Å.

An exemplary process for forming a polycrystalline molybdenum film overa surface of a substrate utilizing an intermediate nucleation film isillustrated with reference to FIG. 2. The exemplary process 200 (FIG. 2)may comprise two distinct deposition processes, a first depositionprocess for depositing a nucleation film directly on an exposed surfaceof a substrate, and a second deposition process for depositing apolycrystalline molybdenum film directly on the nucleation film.

In more detail and with reference to FIG. 2, the exemplary process 200may commence by means of a process block 210 which comprises, providinga substrate into a reaction chamber.

In some embodiments of the disclosure, the substrate may comprise anon-planar substrate including a plurality of non-planar features, asprevious described herein. It should be noted that the embodiments ofthe disclosure are not limited to metal gap-fill methods for fillingvertical non-planar features and horizontal non-planar features and thatother geometries of non-planar features disposed in and/or on asubstrate may be filled with a polycrystalline molybdenum film by theprocesses disclosed herein.

In some embodiments, a non-planar substrate may comprise one or morematerials and material surfaces including, but not limited to,semiconductors, dielectrics, and metallics.

In some embodiments, the substrate may include semiconductor materialsand surfaces, such as, but not limited to, silicon (Si), germanium (Ge),germanium tin (GeSn), silicon germanium (SiGe), silicon germanium tin(SiGeSn), silicon carbide (SiC), or a group III-V semiconductormaterials.

In some embodiments, the substrate may include metallic materials andsurfaces, such as, but not limited to, pure metals, metal nitrides,metal carbides, metal borides, and mixtures thereof.

In some embodiments, the substrate may include dielectric materials andsurfaces, such as, but not limited, to silicon containing dielectricmaterials and metal oxide dielectric materials. In some embodiments, thesilicon containing dielectric materials may comprise one or more of:silicon dioxide (SiO₂), silicon sub-oxides, silicon nitride (Si₃N₄),silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon oxycarbidenitride (SiOCN), silicon carbon nitride (SiCN). In some embodiments, themetal oxide dielectric materials may comprise one or more of: aluminumoxide (Al₂O₃), hafnium oxide (HfO₂), tantalum oxide (Ta₂O₅), zirconiumoxide (ZrO₂), titanium oxide (TiO₂), hafnium silicate (HfSiO_(x)), andlanthanum oxide (La₂O₃).

In some embodiments of the disclosure, the substrate may comprise anengineered substrate wherein a semiconductor layer is disposed over abulk support with an intervening buried oxide (BOX) disposed therebetween.

In some embodiments, the substrates utilized in the processes describedherein may include device structures, including partially fabricateddevice structures, formed into or onto a surface of the substrate. Forexample, a substrate may comprise fabricated and/or partially fabricateddevice structures, such as, for example, transistors and/or memoryelements. In some embodiments, the substrate may contain monocrystallinesurfaces and/or one or more secondary surfaces that may comprise anon-monocrystalline surface, such as a polycrystalline surface and/or anamorphous surface.

The substrate may be loaded into a reaction chamber configured forforming a polycrystalline molybdenum film. In some embodiments, thenucleation film may be deposited directly on an exposed surface of thesubstrate by one or more deposition processes, including, but notlimited to, a chemical vapor deposition (CVD) process, a soak depositionprocess, a plasma-enhanced chemical vapor deposition (PECVD) process, ora physical vapor deposition (PVD) process. In particular embodiments ofthe disclosure, the nucleation film may be deposited employing a firstcyclical deposition process.

In some embodiments, the polycrystalline molybdenum film may bedeposited directly on the nucleation film by a deposition process,including, but not limited to, chemical vapor deposition (CVD) process,a soak deposition process, a plasma-enhanced chemical vapor deposition(PECVD) process, or a physical vapor deposition (PVD) process. Inparticular embodiments of the disclosure, the polycrystalline molybdenumfilm may be deposited employing a second cyclical deposition process.

In some embodiments, the nucleation film and the polycrystallinemolybdenum film may both be deposited employing cyclical depositionprocesses due to the inherent conformality and step coverage achievableemploying cyclical deposition processes, in particular when depositingfilms over non-planar substrates including high aspect ratio features.

Reactor(s) and associated reaction chamber(s) capable of forming thepolycrystalline molybdenum films of the current disclosure may beconfigured for performing cyclical deposition processes, such as, forexample, atomic layer deposition processes (ALD) or cyclical chemicalvapor deposition processes (CCVD). Therefore, in some embodiments, thereactor(s) suitable for performing the embodiments of the disclosure mayinclude ALD reactors, as well as CVD reactors, configured to provide theprecursors. According to some embodiments, a showerhead reactor may beused. According to some embodiments, cross-flow, batch, minibatch, orspatial ALD reactors may be used.

In some embodiments of the disclosure, a batch reactor may be used. Insome embodiments, a vertical batch reactor may be used. For example, avertical batch reactor may comprise a reaction chamber and an elevatorconstructed and arranged to move a boat configured for supporting abatch of between 10 to 200 substrates in or out of the reaction chamber.In other embodiments, a batch reactor comprises a minibatch reactorconfigured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 orfewer wafers, 4 or fewer wafers, or 2 or fewer wafers. In someembodiments in which a batch reactor is used, wafer-to-wafernon-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, oreven less than 0.5%.

The exemplary processes for forming a polycrystalline molybdenum asdescribed herein may optionally be carried out in reactor(s) andassociated reaction chamber(s) connected to a cluster tool. In a clustertool, because each reaction chamber is dedicated to one type of process,the temperature of the reaction chamber in each module can be keptconstant, which improves the throughput compared to a reaction chamberin which the substrate is heated up to the process temperature beforeeach run. Additionally, in a cluster tool it is possible to reduce thetime to pump the reaction chamber to the desired process pressurebetween substrates. In some embodiments, the exemplary processesdisclosed herein may be performed in a cluster tool comprising multiplereaction chambers, wherein each individual reaction chamber may beutilized to expose the substrate to an individual reactant and thesubstrate may be transferred between different reaction chambers forexposure to multiple reactants, the transfer of the substrate beingperformed under a controlled ambient to prevent contamination of thesubstrate and films deposited thereon. For example, the deposition ofthe nucleation film may be performed by a first cyclical depositionprocess in a first reaction chamber associated with a cluster tool andthe deposition of the polycrystalline molybdenum film may be performedby a second cyclical deposition process in a second reaction chamberassociated with the same cluster tool, wherein the transfer ofsubstrates between the first reaction chamber and the second reactionchamber takes place under a controlled environment to preventcontamination. In some embodiments of the disclosure, the processes ofthe current disclosure may be performed in a cluster tool comprisingmultiple reaction chambers, wherein each individual reaction chamber maybe configured to heat the substrate to a different temperature.

In some embodiments, the deposition processes of the current disclosuremay be performed in a single stand-alone reactor which may be equippedwith a load-lock. In such embodiments, it is not necessary to cool downthe reaction chamber between each run. For example, a single stand-alongreactor may be configured to deposit both the nucleation film and thepolycrystalline film, thereby removing the need to transfer substrate(s)between two or more reaction chambers.

Once the substrate is loaded within a suitable reaction chamber, e.g., areaction chamber configured for cyclical deposition processes, theexemplary process 200 for forming a polycrystalline molybdenum film(FIG. 2) may proceed by means of a process block 220 comprising,depositing a nucleation film directly on an exposed surface of thesubstrate, wherein the nucleation film comprises one of a metal oxidenucleation film or a metal nitride nucleation. The process block 220 andit constituent sub-processes are described in more detail with referenceto FIG. 3 which illustrates an exemplary first cyclical depositionprocess for depositing a nucleation film directly on an exposed surfaceof a substrate.

In more detail, a first cyclical deposition process (i.e., process 220of FIG. 3) for depositing a nucleation film directly on an exposedsurface of a substrate may proceed by means of a sub-process block 310comprising, heating the substrate to a desired deposition temperature,i.e., substrate temperature. For example, the substrate may be heated toa deposition temperature of less than approximately 800° C., or lessthan approximately 700° C., or less than approximately 600° C., or lessthan approximately 500° C., or less than approximately 400° C., or lessthan approximately 300° C., or even less than approximately 200° C. Insome embodiments of the disclosure, the substrate temperature during thefirst cyclical deposition process may be between 250° C. and 800° C., orbetween 300° C. and 600° C., or between 550° C. and 600° C.

In some embodiments, the deposition temperature employed for thedeposition of the nucleation film may be dependent on the composition ofthe nucleation film being deposited. For example, in some embodiments ofthe disclosure, the nucleation film may comprise a metal oxidenucleation film, including, but not limited to, an aluminum oxidenucleation film, a molybdenum oxide nucleation film, a tungsten oxidenucleation film, a ruthenium oxide nucleation film, a rhenium oxidenucleation film, or an iridium oxide nucleation film. In such exampleembodiments, the temperature of the substrate during deposition of themetal oxide nucleation film may be less than approximately 800° C., orless than approximately 600° C., or less than approximately 500° C., orless than approximately 400° C., or even less than approximately 300° C.In some embodiments, the temperature of the substrate during thedeposition of the metal oxide nucleation film may be between 250° C. and550° C.

In some embodiments, the nucleation film may comprise a metal nitridenucleation film. For example, the metal nitride nucleation film maycomprise a molybdenum nitride nucleation film. In such exampleembodiments, the temperature of the substrate during deposition of themolybdenum nitride nucleation film may be less than approximately 700°C., or less than approximately 600° C., or less than approximately 500°C., or less than approximately 400° C., or less than approximately 300°C., or even less than 200° C. In some embodiments, the temperature ofthe substrate during the deposition of the molybdenum nitride nucleationfilm may be between 200° C. and 700° C., or between 350° C. and 600° C.,or even between 450° C. and 550° C.

In addition, to achieving a desired deposition temperature, i.e., adesired substrate temperature, the exemplary first cyclical depositionof process block 220 (FIG. 3) may also regulate the pressure within thereaction chamber during the cyclical deposition process to obtain anucleation film with desired characteristics. For example, in someembodiments of the disclosure, the exemplary first cyclical depositionprocess of process block 220 (FIG. 3) may be performed within a reactionchamber regulated to a pressure of less than 300 Torr, or less than 200Torr, or less than 100 Torr, or less than 50 Torr, or less than 25 Torr,or less than 15 Torr, or even less than 2 Torr. In some embodiments, thepressure within the reaction chamber during deposition of the nucleationfilm may be regulated at a pressure between 2 Torr and 300 Torr, orbetween 30 Torr and 80 Torr.

Once the substrate has been heated to a desired temperature and thepressure within the reaction chamber has been regulated to a desiredlevel, the exemplary first cyclical deposition process of process block220 may continue by means of a first cyclical deposition phase 305 whichmay comprise an atomic layer deposition (ALD) process, or cyclicalchemical vapor deposition (CCVD) process.

A non-limiting example embodiment of a cyclical deposition process mayinclude atomic layer deposition (ALD), wherein ALD is based on typicallyself-limiting reactions, whereby sequential and alternating pulses ofreactants are used to deposit about one atomic (or molecular) monolayerof material per unit deposition cycle. The deposition conditions andprecursors are typically selected to provide self-saturating reactions,such that an absorbed layer of one reactant leaves a surface terminationthat is non-reactive with the gas phase reactants of the same reactants.The substrate is subsequently contacted with a different reactant thatreacts with the previous termination to enable continued deposition.Thus, each cycle of alternated pulses typically leaves no more thanabout one monolayer of the desired material. However, as mentionedabove, the skilled artisan will recognize that in one or more ALDdeposition cycles more than one monolayer of material may be deposited,for example, if some gas phase reactions occur despite the alternatingnature of the process.

In some embodiments, a first cyclical deposition process (e.g., an ALDdeposition process) may be utilized for the deposition of the nucleationfilm. For example, the first cyclical deposition process may comprise,performing one or more first unit deposition cycles of the firstcyclical deposition phase 305 (FIG. 3).

In some embodiments of the disclosure, a first unit deposition cycle ofthe first cyclical deposition phase 305 may comprise, exposing thesubstrate to a first vapor phase reactant, removing any unreacted firstvapor phase reactant and reaction byproducts from the reaction chamber,and exposing the substrate to a second vapor phase reactant, followed bya second removal step. In some embodiments of the disclosure, the firstvapor phase reactant may comprise a metal precursor and the second vaporphase reactant may comprise one of a nitrogen precursor, or an oxygenprecursor.

In some embodiments, precursors may be separated by inert gases, such asargon (Ar) or nitrogen (N₂), to prevent gas-phase reactions betweenreactants and enable self-saturating surface reactions. In someembodiments, however, the substrate may be moved to separately contact afirst vapor phase reactant and a second vapor phase reactant. Becausethe reactions self-saturate, strict temperature control of thesubstrates and precise dosage control of the precursors may not berequired. However, the substrate temperature is preferably such that anincident gas species does not condense into monolayers nor decompose onthe surface. Surplus precursor and reaction byproducts, if any, areremoved from the substrate surface, such as by purging the reactionchamber or by moving the substrate, before the substrate is contactedwith the next reactant. Undesired gaseous molecules can be effectivelyexpelled from the reaction chamber with the help of an inert purginggas. A vacuum pump may be used to assist in the purging of the reactionchamber.

According to some non-limiting embodiments of the disclosure, ALDprocesses may be used to deposit a nucleation film directly on anexposed surface of a substrate. In some embodiments of the disclosure,the cyclical deposition phase 305 of an ALD process employed fordepositing a nucleation film may comprise a first unit deposition whichmay include two distinct deposition stages. In a first stage of thefirst unit deposition cycle the substrate may be contacted with a metalprecursor, forming no more than about one monolayer of reactant specieson the surface of the substrate. In a second stage of the first unitdeposition cycle, the substrate may be contacted with one of a nitrogenprecursor or an oxygen precursor.

Therefore, in some embodiments, the first cyclical deposition phase 305of the first cyclical deposition process 220 (FIG. 3) may proceed bymeans of a sub-process block 320, which comprises contacting thesubstrate with a first vapor phase reactant and in particularlyembodiments, contacting the substrate with a first vapor phase reactantcomprising a metal precursor.

In some embodiments, the nucleation film may comprise a metal oxidenucleation film. For example, the metal oxide nucleation film maycomprise at least one of: an aluminum oxide nucleation film, amolybdenum oxide nucleation film, a tungsten oxide nucleation film, aruthenium oxide nucleation film, a rhenium oxide nucleation film, or aniridium oxide nucleation film.

In some embodiments, the nucleation film may comprise an aluminum oxidenucleation film and in such embodiments the metal precursor, i.e., thealuminum precursor, may comprise at least one of: trimethylaluminum(TMA), triethylaluminum (TEA), dimethylaluminumhydride (DMAH),tritertbutylaluminum (TTBA), aluminum trichloride (AlCl₃), ordimethylaluminumisopropoxide (DMAI).

In some embodiments, the nucleation film may comprise a tungsten oxidenucleation film and in such embodiments the metal precursor, i.e., thetungsten precursor, may comprise a metalorganic tungsten precursor. Insome embodiments, the metalorganic tungsten precursor may comprise,cyclopentadienyl compounds of tungsten, tungsten betadiketonatecompounds, tungsten alkylamine compounds, tungsten amidinate compounds,or other metalorganic tungsten compounds. In some embodiments, themetalorganic tungsten precursor may comprise,bis(tert-butylimino)bis(tertbutylamino)tungsten(VI),bis(isopropylcyclopentadienyl)tungsten(IV)dihydride, ortetracarbonyl(1,5-cyclooctadiene)tungsten(0).

In some embodiments, the nucleation film may comprise a ruthenium oxidenucleation film and in such embodiments the metal precursor, i.e., theruthenium precursor, may comprise at least one of: ruthenium tetraoxide(RuO₄), Bis(cyclopentadienyl)ruthenium(II),Bis(ethylcyclopentadienyl)ruthenium(II), and trirutheniumdodecacarbonyl.

In some embodiments, the nucleation film may comprise a rhenium oxidenucleation film and in such embodiments the metal precursor, i.e., therhenium precursor, may comprise at least one of a rhenium halideprecursor, a rhenium oxyhalide precursor, an alkyl rhenium oxideprecursor, a cyclopentadienyl based rhenium precursor, or a rheniumcarbonyl halide precursor. Further information relating to rheniumprecursors is described in U.S. patent application Ser. No. 16/219,555entitled “Methods for forming a rhenium-containing film on a substrateby a cyclical deposition process and related semiconductor devicestructure” the entire contents of which is incorporated by referenceherein.

In some embodiments, the nucleation film may comprise an iridium oxidenucleation film and in such embodiments the metal precursor, i.e. theiridium precursor, may comprise at least one of:1,5-Cyclooctadiene(acetylacetonato)iridium(I),1,5-Cyclooctadiene(hexafluoroacetylacetonato)iridium(I),1-Ethylcyclopentadienyl-1,3-cyclohexadieneiridium(I),Iridium(II)acetylacetonate,(Methylcyclopentadienyl)(1,5-cyclooctadiene)iridium(I), andTris(norbornadiene)(acetylacetonato)iridium(III).

In some embodiments, the nucleation film may comprise a molybdenum oxidenucleation film and in such embodiments, the metal precursor, i.e., themolybdenum precursor may comprise a molybdenum halide precursor. In someembodiments, the molybdenum halide precursor may comprise a molybdenumchloride precursor, a molybdenum iodide precursor, or a molybdenumbromide precursor. As non-limiting examples, the molybdenum halideprecursor may comprise at least one of: molybdenum pentachloride(MoCl₅), molybdenum, hexachloride (MoCl₆), molybdenum hexafluoride(MoF₆), molybdenum triiodide (MoI₃), or molybdenum dibromide (MoBr₂). Insome embodiments, the molybdenum halide precursor may comprise amolybdenum chalcogenide and in particular embodiments the molybdenumhalide precursor may comprise a molybdenum chalcogenide halide. Forexample, the molybdenum chalcogenide halide precursor may comprise amolybdenum oxyhalide selected from the group comprising: a molybdenumoxychloride, a molybdenum oxyiodide, or a molybdenum oxybromide. Inparticular embodiments of the disclosure, the molybdenum halideprecursor may comprise a molybdenum oxychloride, including, but notlimited to, molybdenum (V) trichloride oxide (MoOCl₃), molybdenum (VI)tetrachloride oxide (MoOCl₄), or molybdenum (IV) dichloride dioxide(MoO₂Cl₂).

In alternative embodiments, the molybdenum precursor, may comprise ametalorganic molybdenum precursor, such as, for example, Mo(CO)₆,Mo(tBuN)₂(NMe₂)₂, Mo(NBu)₂(StBu)₂, (Me₂N)₄Mo, and (iPrCp)₂MoH₂.

In some embodiments, the nucleation film may comprise a metal nitridenucleation film. For example, the metal nitride nucleation film maycomprise a molybdenum nitride nucleation film. In such embodimentswherein the metal nitride nucleation film comprises a molybdenum nitridenucleation film the metal precursor, i.e., the molybdenum precursor maycomprise a molybdenum halide, examples of which have previouslydescribed herein. In particular embodiments of the disclosure, themolybdenum precursor may comprise a molybdenum oxychloride, including,but not limited to, molybdenum (V) trichloride oxide (MoOCl₃),molybdenum (VI) tetrachloride oxide (MoOCl₄), or molybdenum (IV)dichloride dioxide (MoO₂Cl₂). In alternative embodiments, the molybdenumprecursor may comprise a molybdenum metalorganic as previously describedherein.

In some embodiments, the nucleation film may comprise a metal silicidenucleation film or a metal boride nucleation film, such as, for example,a molybdenum silicide nucleation film or a molybdenum boride nucleationfilm. For example, metal silicide nucleation films may be depositedemploying a silicon containing precursor, such as, for example, silane(SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), tetrasilane (Si₄H₁₀) orhigher order silanes with the general empirical formulaSi_(x)H_((2x+2)). In addition examples, metal boride nucleation filmsmay be deposited employing a boron containing precursor, such as, forexample, borane (BH₃), diborane (B₂H₆), or other boranes, such asdecaborane (B₁₀H₁₄).

In some embodiments, contacting the substrate with the metal precursormay comprise a contact time period of between about 0.1 seconds andabout 60 seconds, or between about 0.1 seconds and about 10 seconds, orbetween about 0.5 seconds and about 5.0 seconds. In addition, during thecontacting of the substrate with the metal precursor, the flow rate ofthe metal precursor may be less than 1000 sccm, or less than 500 sccm,or less than 100 sccm, or less than 10 sccm, or even less than 1 sccm.In addition, during the contacting of substrate with the metalprecursor, the flow rate of the metal precursor may range from about 1to 2000 sccm, from about 5 to 1000 sccm, or from about 10 to about 500sccm.

The first cyclical deposition phase 305 of the first cyclical depositionprocess 220 (FIG. 3) may continue by purging the reaction chamber. Forexample, excess metal precursor and reaction byproducts (if any) may beremoved from the surface of the substrate, e.g., by pumping with aninert gas. In some embodiments of the disclosure, the purge process maycomprise a purge cycle wherein the substrate surface is purged for atime period of less than approximately 5.0 seconds, or less thanapproximately 3.0 seconds, or even less than approximately 2.0 seconds.Excess metal precursor and any possible reaction byproducts may beremoved with the aid of a vacuum, generated by a pumping system in fluidcommunication with the reaction chamber.

Upon purging the reaction chamber with a purge cycle the first cyclicaldeposition phase 305 of the first cyclical deposition process 220 (FIG.3) may continue by means of a sub-process block 330 which comprises,contacting the substrate with a second vapor phase reactant, andparticularly contacting the substrate with one of a nitrogen precursor,or an oxygen precursor.

In some embodiments, the nucleation film may comprise a metal oxidenucleation film and in such embodiments, the first vapor phase reactantmay comprise a metal precursor and the second vapor phase reactant maycomprise an oxygen precursor. In some embodiments, the nucleation filmmay comprise a metal nitride nucleation film and in such embodiments,the first vapor phase reactant may comprise a metal precursor and thesecond vapor phase reactant may comprise a nitrogen precursor.

In embodiments of disclosure employing a metal oxide nucleation film,the second vapor phase reactant may comprise one or more of the oxygenprecursor selected from the group comprising: water (H₂O), hydrogenperoxide (H₂O₂), ozone (O₃), or oxides of nitrogen, such as, forexample, nitrogen monoxide (NO), nitrous oxide (N₂O), or nitrogendioxide (NO₂). As further non-limiting examples, the oxygen precursormay comprise: an organic alcohol, such as, for example, isopropylalcohol, or an oxygen plasma, wherein the oxygen plasma may comprise:atomic oxygen, oxygen radicals, and excited oxygen species.

In embodiments of the disclosure employing a metal nitride nucleationfilm, the second vapor phase reactant may comprise a nitrogen precursor.For example, the nitrogen precursor may comprise at least one of:ammonia (NH₃), hydrazine (N₂H₄), triazane (N₃H₅), tertbutylhydrazine(C₄H₉N₂H₃), methylhydrazine (CH₃NHNH₂), dimethylhydrazine ((CH₃)₂N₂H₂),or a nitrogen plasma, wherein the nitrogen plasma includes: atomicnitrogen, nitrogen radicals, and excited nitrogen species.

In some embodiments of the disclosure, contacting the substrate with thesecond vapor phase reactant, i.e., the oxygen precursor, or the nitrogenprecursor, may comprise, contacting the substrate with the precursor fora time period of between about 0.01 seconds and about 120 seconds,between about 0.05 seconds and about 60 seconds, or between about 0.1seconds and about 10 seconds. In addition, during the contacting of thesubstrate with the second vapor phase reactant, the flow rate of thesecond vapor phase reactant may be less than 10000 sccm, or less than5000 sccm, or even less than 100 sccm.

Upon contacting the substrate with one of a nitrogen precursor, or anoxygen precursor, the first cyclical deposition phase 305 of processblock 220 (FIG. 3) may proceed by purging the reaction chamber. Forexample, excess second vapor phase reactant and reaction byproducts (ifany) may be removed from the surface of the substrate, as previouslydescribed herein.

Upon completion of the purge of the second vapor phase reactant and anyreaction byproducts from the reaction chamber, the first cyclicdeposition phase 305 of the first cyclical deposition process 220 (FIG.3) may continue with a decision gate 340, wherein the decision gate 340is dependent on the desired average film thickness of the depositednucleation film. For example, if the nucleation film is deposited at aninsufficient thickness for a desired application, then the cyclicaldeposition phase 305 may be repeated by returning to the sub-processblock 320 and continuing through a further first unit deposition cycle,wherein a first unit deposition cycle may comprise, contacting thesubstrate with a metal precursor (sub-process block 320), purging thereaction chamber, contacting the substrate with one of a nitrogenprecursor, or an oxygen precursor (sub-process block 330), and againpurging the reaction chamber. A first unit deposition cycle of cyclicaldeposition phase 305 may be repeated one or more times until a desiredaverage thickness of the nucleation film is deposited over thesubstrate. Once the nucleation film has been deposited to the desiredaverage thickness the first cyclical deposition process of process block220 may exit via a sub-process block 350 and the substrate with thenucleation film deposited thereon, may be subjected to the furtherprocesses of the polycrystalline molybdenum film formation process 200of FIG. 2.

It should be appreciated that in some embodiments of the disclosure, theorder of contacting of the substrate with the first vapor phase reactant(e.g., the metal precursor) and the second vapor phase reactant (e.g.,the nitrogen precursor, or oxygen precursor) may be such that thesubstrate is first contacted with the second vapor phase reactantfollowed by the first vapor phase reactant. In addition, in someembodiments, the cyclical deposition phase 305 of the first cyclicaldeposition process 220 may comprise, contacting the substrate with thefirst vapor phase reactant one or more times prior to contacting thesubstrate with the second vapor phase reactant one or more times. Inaddition, in some embodiments, the cyclical deposition phase 305 ofexemplary process 220 may comprise, contacting the substrate with thesecond vapor phase reactant one or more times prior to contacting thesubstrate with the first vapor phase reactant one or more times.

In embodiments wherein the nucleation film comprises a molybdenumnitride film, the cyclical deposition phase 305 may additional include,contacting the substrate with a third vapor phase reactant comprising areducing agent. For example, the nitrogen precursor and the reducingagent may be introduced into reaction chamber simultaneously oralternatively the nitrogen precursor and the reducing agent may beintroduced into the reaction chamber separately with or without anintervening purge cycle. Further information relating to methods fordepositing a molybdenum nitride film is described in U.S. ApplicationNo. 62/891,254 entitled “Methods for depositing a molybdenum nitridefilm on a surface of a substrate by a cyclical deposition process andrelated semiconductor device structure,” Stevens et al., the entirecontents of which is incorporated by reference herein.

In some embodiments, the first cyclical deposition process as describedherein may comprise a hybrid ALD/CVD process or a cyclical CVD process.For example, in some embodiments, the deposition rate of the firstcyclical deposition process (e.g., an ALD process) may be low comparedwith the deposition rate of a CVD process. One exemplary approach toincrease the deposition rate of the first cyclical deposition processmay be that of operating at a higher substrate temperature than thattypically employed in an ALD process, resulting in some portion of a CVDprocess, but still taking advantage of the sequential introduction ofprecursors, such a process may be referred to as cyclical CVD. In someembodiments, a cyclical CVD process may comprise the introduction of twoor more precursors into the reaction chamber wherein there may be a timeperiod of overlap between the two or more precursors in the reactionchamber resulting in both an ALD deposition component and a CVDdeposition component. For example, a cyclical CVD process may comprisethe continuous flow of a one precursor and the periodic pulsing of asecond precursor into the reaction chamber.

In some embodiments of the disclosure, the nucleation film may bedeposited directly on an exposed surface of the substrate at a growthrate from about 0.05 Å/cycle to about 5 Å/cycle, or from about 0.1Å/cycle to about 2 Å/cycle.

In some embodiments of the disclosure, the nucleation film may bedeposited as a physically continuous film. For example, the thickness atwhich a film becomes physically continuous may be determined utilizinglow-energy ion scattering (LEIS). In some embodiments, a physicallycontinuous nucleation film may be deposited to an average film thicknessof less than 100 Å, or less than 50 Å, or less than 40 Å, or less than30 Å, or less than 20 Å, or less than 10 Å, or even less than 5 Å. Insome embodiments, a physically continuous nucleation film may bedeposited to an average film thickness between approximately 5 Å and 50Å.

In some embodiments of the disclosure, the nucleation film is depositedas a physically discontinuous film having an average film thickness ofless than 50 Å, or less than 40 Å, or less than 30 Å, or less than 20 Å,or less than 10 Å, or less than 5 Å, or less than 2 Å, or even less than1 Å. In some embodiments, the physically discontinuous nucleation filmmay be deposited to an average film thickness between approximately 1 Åand 50 Å

In some embodiments of the disclosure, the nucleation film may bedeposited as an amorphous film. For example, the nucleation film maycomprise one of an amorphous metal oxide film or an amorphous metalnitride film.

In some embodiments, the exposed surface of the substrate may comprise aplurality of non-planar features, e.g., vertical non-planar featuresand/or horizontal non-planar features. As a non-limiting example, thesurface of the substrate may comprise a plurality of vertical trenches(e.g., v-shaped vertical trenches, or tapered vertical trenches) and thestep coverage of the nucleation film deposited over the non-planarsurface of the substrate may be greater than about 50%, or greater thanabout 80%, or greater than about 90%, or greater than about 95%, orgreater than about 98%, or even greater than about 99%. In someembodiments, the non-planar features may comprise a vertical non-planarfeatures having an aspect ratio, e.g., the ratio of the height of avertical trench to the width of a vertical trench, which may be greaterthan 2:1, or greater than 5:1, or greater than 10:1, or greater than25:1, or greater than 50:1, or even greater than 100:1, wherein “greaterthan” as used in this example refers to a greater height of a verticalnon-planar feature. In some embodiments, the substrate may comprise onemore horizontal non-planar features, wherein the horizontal non-planarfeatures may have an aspect ratio (height:width) which may be greaterthan 1:2, or greater than 1:5, or greater than 1:10, or greater than1:25, or greater than 1:50, or even greater than 1:100, wherein “greaterthan” as used in this example refers to a greater distance in the widthof the horizontal non-planar feature.

It should also be noted that the nucleation films of the currentdisclosure do not constitute a barrier layer or barrier material ascommonly used in semiconductor device applications to prevent diffusionof metal species into an underlying dielectric material. The nucleationfilms of the current disclosure are utilized to improve the materialqualities of a subsequently deposited polycrystalline molybdenum filmand do not constitute the high resistivity barrier layers or barriermaterials employed in common semiconductor device fabrication processes.

In some embodiments, employing the nucleation films of the currentdisclosure may improve the subsequent processes for depositing apolycrystalline molybdenum film directly on the nucleation film. Forexample, utilizing a nucleation film prior to the deposition of thepolycrystalline molybdenum film may increase the workable process windowfor high quality film deposition, i.e., the deposition process is lesssensitive to a variability in process parameters (e.g., depositiontemperature, pressure, pulse period, cycle time, etc.).

After depositing the nucleation film directly on an exposed surface ofthe substrate, the exemplary polycrystalline molybdenum film formationprocess 200 (FIG. 2) may continue by means of a process block 230comprising, depositing a polycrystalline molybdenum film directly on thenucleation film.

In more detail, the process block 230 employed for depositing thepolycrystalline molybdenum film may comprise a second cyclicaldeposition process. In some embodiments, the process block 230 mayemploy alternative deposition methods as previous described herein. Theprocess block 230 and the related constituent sub-process blocks aredescribed in greater detail with reference to FIG. 4, which illustratesa second cyclical deposition process for depositing a polycrystallinemolybdenum film.

In some embodiments, the second cyclical deposition process 230 of FIG.4 may comprise an atomic layer deposition process or a cyclical chemicalvapor deposition process, as previously described herein. As anon-limiting example, the second cyclical deposition process 230 maycomprise an ALD process which may commence by means of a sub-processblock 410 comprising, heating the substrate to a desired depositiontemperature. For example, the substrate may be heated to a substratetemperature of less than approximately 800° C., or less thanapproximately 700° C., or less than approximately 600° C., or less thanapproximately 500° C., or less than approximately 400° C., or less thanapproximately 300° C., or even less than approximately 200° C. In someembodiments of the disclosure, the substrate temperature during thesecond cyclical deposition 230 may be between 200° C. and 800° C., orbetween 300° C. and 700° C., or between 400° C. and 600° C., or between500° C. and 550° C.

In addition, to achieving a desired deposition temperature, i.e., adesired substrate temperature, the second cyclical deposition process230 may also regulate the pressure within the reaction chamber duringthe deposition process to obtain desirable characteristics of thedeposited polycrystalline molybdenum film. For example, in someembodiments of the disclosure, the second cyclical deposition process230 may be performed within a reaction chamber regulated to a pressureof less than 300 Torr, or less than 200 Torr, or less than 100 Torr, orless than 50 Torr, or less than 25 Torr, or even less than 10 Torr. Insome embodiments, the pressure within the reaction chamber duringdeposition may be regulated at a pressure between 10 Torr and 300 Torr,or between 30 Torr and 80 Torr, or even equal to or greater than 30Torr.

Upon heating the substrate to a desired deposition temperature andregulating the pressure within the reaction chamber, the second cyclicaldeposition process 230 (FIG. 4) may continue with a second cyclicaldeposition phase 405. The second cyclical deposition phase 405 mayproceed by means of a sub-process block 420 which comprises, contactingthe substrate with a third vapor phase reactant which may comprise amolybdenum halide precursor.

In some embodiments, the molybdenum halide precursor may comprise amolybdenum chloride precursor, a molybdenum iodide precursor, or amolybdenum bromide precursor. For example, the molybdenum halideprecursor may comprise one or more of: molybdenum pentachloride (MoCl₅),molybdenum, hexachloride (MoCl₆), molybdenum hexafluoride (MoF₆),molybdenum triiodide (MoI₃), or molybdenum dibromide (MoBr₂). Inparticular embodiments, the molybdenum halide precursor may comprise amolybdenum chloride precursor, such as, for example, molybdenumpentachloride (MoCl₅), or molybdenum hexachloride (MoCl₆).

In alternative embodiments, the molybdenum precursor, may comprise ametalorganic molybdenum precursor, such as, for example, Mo(CO)₆,Mo(tBuN)₂(NMe₂)₂, Mo(NBu)₂(StBu)₂, (Me₂N)₄Mo, and (iPrCp)₂MoH₂.

In some embodiments, the molybdenum halide precursor may comprise amolybdenum chalcogenide halide precursor. For example, the molybdenumchalcogenide halide precursor may comprise a molybdenum oxyhalideselected from the group comprising: a molybdenum oxychloride, amolybdenum oxyiodide, or a molybdenum oxybromide. In particularembodiments of the disclosure, the molybdenum halide precursor maycomprise a molybdenum oxychloride, including, but not limited to,molybdenum (V) trichloride oxide (MoOCl₃), molybdenum (VI) tetrachlorideoxide (MoOCl₄), or molybdenum (IV) dichloride dioxide (MoO₂Cl₂).

In some embodiments of the disclosure, the substrate may be contactedwith a molybdenum halide precursor for a time period of between about0.1 seconds and about 60 seconds, or between about 0.1 seconds and about10 seconds, or between about 0.5 seconds and about 5.0 seconds. Inaddition, during the contacting of the substrate with the molybdenumhalide precursor, the flow rate of the molybdenum halide precursor maybe less than 1000 sccm, or less than 500 sccm, or less than 100 sccm, orless than 10 sccm, or even less than 1 sccm. In addition, during thecontacting of substrate with the molybdenum halide precursor, the flowrate of the molybdenum precursor may range from about 1 to 2000 sccm,from about 5 to 1000 sccm, or from about 10 to about 500 sccm.

The second cyclical phase 405 of the second cyclical deposition process230 (FIG. 4) may continue by purging the reaction chamber. For example,excess molybdenum halide precursor and reaction byproducts (if any) maybe removed from the surface of the substrate, e.g., by pumping with aninert gas. In some embodiments of the disclosure, the purge process maycomprise one or more purge cycles as previously described herein.

Upon purging the reaction chamber the second cyclical deposition 405 maycontinue by means of a sub-process block 430 which comprises, contactingthe substrate with a fourth vapor phase reactant which may comprise areducing agent. For example, the reducing agent may comprise at leastone of: forming gas (H₂+N₂), ammonia (NH₃), hydrazine (N₂H₄), analkyl-hydrazine (e.g. tertiary butyl hydrazine (C₄H₁₂N₂)), molecularhydrogen (H₂), hydrogen atoms (H), a hydrogen plasma, hydrogen radicals,hydrogen excited species, an alcohol, an aldehyde, a carboxylic acid, aborane, or an amine. In further examples, the reducing agent maycomprise at least one of: silane (SiH₄), disilane (Si₂H₆), trisilane(Si₃H₈), germane (GeH₄), digermane (Ge₂H₆), borane (BH₃), or diborane(B₂H₆). In particular embodiments of the disclosure, the reducing agentmay comprise molecular hydrogen (H₂).

In some embodiments of the disclosure, the substrate may be contactedwith the reducing agent for a time period of between about 0.01 secondsand about 180 seconds, or between about 0.05 seconds and about 60seconds, or between about 0.1 seconds and about 10.0 seconds. Inaddition, during the contacting of the substrate with the reducingagent, the flow rate of the reducing agent may be less than 30 slm, orless than 15 slm, or less than 10 slm, or less than 5 slm, or less than1 slm, or even less than 0.1 slm. In addition, during the contacting ofthe substrate with the reducing agent, the flow rate of the reducingagent may range from about 0.1 to 30 slm, from about 5 to 15 slm, orequal to or greater than 10 slm.

Upon contacting the substrate with the reducing agent, the secondcyclical deposition phase 405 may proceed by purging the reactionchamber, as described previously herein.

Upon completion of the purge of the reducing agent (and any reactionbyproducts) from the reaction chamber, the second cyclic depositionphase 405 may continue with a decision gate 440, wherein the decisiongate 440 is dependent on the desired average thickness of the depositedpolycrystalline molybdenum film. For example, if the polycrystallinemolybdenum metal is deposited at an insufficient average thickness for adesired application, then the cyclical deposition phase 405 may berepeated by returning to the sub-process block 420 and continuingthrough a further second unit deposition cycle, wherein a second unitdeposition cycle of the second cyclical deposition process 230 maycomprise, contacting the substrate with a molybdenum halide precursor(sub-process block 420), purging the reaction chamber, contacting thesubstrate with a reducing agent (sub-process block 430), and againpurging the reaction chamber. A second unit deposition cycle of cyclicaldeposition phase 405 may be repeated one or more times until a desiredaverage thickness of the polycrystalline molybdenum metal is depositeddirectly on the nucleation film. Once the polycrystalline molybdenumfilm has been deposited to the desired average thickness the secondcyclical deposition process 230 may exit via a sub-process block 450.

Upon completion of the process for depositing the polycrystallinemolybdenum film (process block 230), the exemplary process 200 (of FIG.2) employed for the formation of a polycrystalline molybdenum film mayconclude via the process block 240, wherein the process exits and thesubstrate with the polycrystalline molybdenum film disposed thereon maybe subjected to further processes to fabrication a desired structure,such as a semiconductor device structure, for example.

It should be appreciated that in some embodiments of the disclosure, theorder of contacting of the substrate with the molybdenum precursor andthe reducing agent may be such that the substrate is first contactedwith the reducing agent followed by the molybdenum precursor. Inaddition, in some embodiments, the cyclical deposition phase 405 of thesecond cyclical deposition process 230 may comprise, contacting thesubstrate with the molybdenum precursor one or more times prior tocontacting the substrate with the reducing agent one or more times. Inaddition, in some embodiments, the cyclical deposition phase 405 of thesecond cyclical deposition process block 230 may comprise, contactingthe substrate with the reducing agent one or more times prior tocontacting the substrate with the molybdenum precursor one or moretimes.

In some embodiments, the second cyclical deposition process 230 utilizedfor the deposition of the polycrystalline molybdenum film may comprise ahybrid ALD/CVD process or a cyclical CVD process, as previouslydescribed herein.

The polycrystalline molybdenum films deposited by the methods disclosedherein may be a physically continuous films. In some embodiments, thepolycrystalline molybdenum films may be physically continuous at anaverage film thickness of less than approximately 100 Å, or less thanapproximately 60 Å, or less than approximately 50 Å, or less thanapproximately 40 Å, or less than approximately 30 Å, or less thanapproximately 20 Å, or even less than approximately 10 Å.

In some embodiments of the disclosure, the polycrystalline molybdenumfilm may have an average film thickness from approximately 20 Å to 250Å, or from approximately 50 Å to 200 Å, or even from approximately 100 Åto 150 Å. In some embodiments, the polycrystalline molybdenum films mayhave an average film thickness greater than approximately 20 Å, orgreater than approximately 30 Å, or greater than approximately 40 Å, orgreater than approximately 50 Å, or greater than approximately 60 Å, orgreater than approximately 100 Å, or greater than approximately 250 Å,or even greater than approximately 500 Å. In some embodiments, thepolycrystalline molybdenum films may have an average film thickness ofless than approximately 250 Å, or less than approximately 100 Å, or lessthan approximately 50 Å, or less than approximately 25 Å, or less thanapproximately 10 Å, or even less than approximately 5 Å. In someembodiments, the polycrystalline molybdenum films of the currentdisclosure may have an average film thickness between approximately 100Å and 250 Å.

In some embodiments, the polycrystalline molybdenum films may comprise aplurality of molybdenum crystallites (also referred to as molybdenumgrains), wherein the plurality of molybdenum crystallites may comprisemicroscale, or even nanoscale regions of crystalline molybdenum formingthe polycrystalline molybdenum film. In some embodiments, the molybdenumcrystallites formed by the methods disclosed herein may have an averagecrystallite size of less than 100 Å, or less 80 Å, or less than 60 Å, orless than 40 Å, or less than 20 Å, or even less than 10 Å. In someembodiments, the molybdenum crystallites may have an average crystallitesize between approximately 10 Å and 100 Å, or between approximately 20 Åand 75 Å, or even between approximately 25 Å and 50 Å. As a non-limitingexample, a polycrystalline molybdenum film may be deposited directly ona molybdenum nitride nucleation film and the molybdenum crystallites ofthe polycrystalline molybdenum metal may have an average crystallitesize of less than approximately 60 Å, or less than approximately 50 Å,or even less than approximately 40 Å. The average size of the pluralityof molybdenum crystallites may be determined by x-ray diffraction (XRD)measurements.

In some embodiments, the average crystallite size of the polycrystallinemolybdenum film may be adjusted by altering the properties of theunderlying nucleation film, such as, for example, surface roughness,composition, and average crystallite size.

In some embodiments, the use of an intermediate nucleation film mayimprove the surface roughness of a polycrystalline molybdenum filmsubsequently deposited directly on the nucleation film. For example, thepolycrystalline molybdenum films formed according to the embodiments ofthe disclosure may have a r.m.s. surface roughness (R_(a)) of less than5 Å, or less than 3 Å, or less than 2 Å, or even less than 1 Å. In someembodiments, the r.m.s. surface roughness (R_(a)) of the polycrystallinemolybdenum films may be between approximately 1 Å and 10 Å, or betweenapproximately 2 Å and 5 Å, or even between approximately 2 Å and 3 Å.

In some embodiments, the surface roughness of the polycrystallinemolybdenum films may be expressed as a percentage roughness of theaverage total thickness of the polycrystalline molybdenum film. Forexample, the percentage surface roughness of the polycrystallinemolybdenum films may be less than 10%, or less than 5%, or less 3%, oreven less than 1%. As a non-limiting example, the nucleation film maycomprise a molybdenum nitride nucleation film having an average filmthickness of approximately 20 Å, and a polycrystalline molybdenum filmdeposited directly on the molybdenum nitride nucleation may have anaverage film thickness of approximately 100 Å, wherein thepolycrystalline molybdenum film has a r.m.s. surface roughness (R_(a))of less than 4 Å and a corresponding percentage surface roughness ofless than 4%.

In some embodiments, the substrate may comprise a dielectric materialand the nucleation film may be deposited directly on an exposed surfaceof the dielectric material. In some embodiments, the substrate maycomprise a metallic material and the nucleation film may be depositeddirectly on an exposed surface of the metallic material. In someembodiments, the substrate may comprise a semiconductor material and thenucleation film may be deposited directly on an exposed surface of thesemiconductor material.

The embodiments of the current disclosure employing an intermediatenucleation film between the surface of a substrate and a polycrystallinemolybdenum film may result in a higher quality polycrystallinemolybdenum film than would be otherwise be formed by deposition of apolycrystalline molybdenum film directly on an exposed surface of asubstrate, i.e., without employing an intermediate nucleation film.

As a non-limiting example, the exposed surface of the substrate maycomprise an aluminum oxide (e.g., Al₂O₃) surface and a molybdenumnitride nucleation film may be deposited directly on an exposed surfaceof the aluminum oxide to an average nucleation film thickness of lessthan 25 Å. Following the deposition of the molybdenum nitride nucleationfilm, a polycrystalline molybdenum film may be deposited directly on themolybdenum nitride nucleation film. In such an example, thepolycrystalline molybdenum film may have a r.m.s. surface roughness(R_(a)) of less than 5 Å, or less 4 Å, or less than 3 Å, or even lessthan 2 Å. In addition, the polycrystalline molybdenum film of such anexample may have a percentage surface roughness of less than 5%, or lessthan 4%, or less 3%, or even less than 2%.

In some embodiment, the substrate may comprise a dielectric material andthe nucleation film may be deposited directly on an exposed surface ofthe dielectric material. In some embodiment, the substrate may comprisea semiconductor material and the nucleation film may be depositeddirectly on an exposed surface of the semiconductor material. In someembodiment, the substrate may comprise a metallic material and thenucleation film may be deposited directly on an exposed surface of themetallic material. In some embodiments, the nucleation film may bedeposited direct on an exposed surface of non-planar substrate whereinthe exposed surface may comprise one or more of: a dielectric surface, asemiconductor surface, or a metallic surface. As a non-limiting example,the nucleation film may comprise a molybdenum nitride nucleation filmdeposited directly over one or more of a dielectric surface, a metallicsurface, or a semiconductor surface.

In some embodiments, the polycrystalline molybdenum film disposeddirectly on the nucleation film constitutes a bilayer having a lowelectrical resistivity. For example, a bilayer formed according to theembodiments of the disclosure may have an electrical resistivity of lessthan 50 μΩ-cm, or less than 30 μΩ-cm, or less than 20 μΩ-cm, or evenless than 25 μΩ-cm, wherein the bilayer may comprise an averagenucleation film thickness of less than 20 Å and an averagepolycrystalline molybdenum film thickness of less than 100 Å.

As a non-limiting example, the bilayer may be deposited directly on adielectric material, i.e., by deposition of the nucleation film directlyon an exposed surface of a dielectric material, and deposition of thepolycrystalline molybdenum film directly on the nucleation film. In suchan example, the bilayer may have an electrical resistivity of less than50 μΩ-cm, or less than 30 μΩ-cm, or less than 20 μΩ-cm, or even lessthan 25 μΩ-cm, wherein the bilayer may comprise an average nucleationfilm thickness of less than 20 Å and an average polycrystallinemolybdenum film thickness of less than 100 Å.

In some embodiments, the exposed surface of the nucleation film, uponwhich the polycrystalline molybdenum film is deposited, may comprise aplurality of non-planar features, e.g., vertical non-planar featuresand/or horizontal non-planar features. As a non-limiting example, thesurface of the nucleation film may comprise a plurality of verticaltrenches (e.g., v-shaped vertical trenches, or tapered verticaltrenches) and the step coverage of the polycrystalline molybdenum filmdeposited directly over the non-planar surface of the nucleation filmmay be greater than about 50%, or greater than about 80%, or greaterthan about 90%, or greater than about 95%, or greater than about 98%, oreven greater than about 99%. In some embodiments, the non-planarfeatures of the nucleation film may comprise vertical non-planarfeatures having an aspect ratio, e.g., the ratio of the height of avertical trench to the width of a vertical trench, which may be greaterthan 2:1, or greater than 5:1, or greater than 10:1, or greater than25:1, or greater than 50:1, or even greater than 100:1, wherein “greaterthan” as used in this example refers to a greater height of a verticalnon-planar feature.

The polycrystalline molybdenum films formed by the deposition methodsdisclosed herein may be utilized in a number of applications. Forexample, applications may include, but are not limited to, logic andmemory contact fill, DRAM buried wordline (bWL) fill, verticallyintegrated memory gate/wordline fill, as well as 3D-intergrationprocesses, such as, through-silicon-via fill. The molybdenum gap-fillprocesses of the current disclosure may also be utilized to fillhorizontal non-planar features, such as, a 3D-NAND wordline.

The deposition methods and polysilicon molybdenum films disclosed hereinmay be beneficial in the example applications described above due to thelow electrical resistivity of polysilicon molybdenum films, even in thinfilm applications. The disadvantage of current metal gap-fill films,such as, tungsten films, include: high electrical resistivity nucleationlayers, high electrical resistivity barrier layers, and an undesirableincrease in electrical resistivity as thinner nucleation films andbarrier layers are required as device feature size decreases.Substitution of thin high resistivity films with the nucleation filmsand polycrystalline molybdenum films of the current disclosure may allowfor reduced power losses and reduced heating in integrated circuitapplications.

An additional disadvantage of current metal gap-fill processes andmaterials is the occurrence of “line bending” which may be observed, forexample, in substrates having numerous non-planar features with a narrowpitch, or in substrates having numerous high aspect ratio non-planarfeatures adjacent to one another (as described previously herein withreference to FIGS. 1A-B). Significant line bending has been observed inDRAM buried wordline structures (bWL) when employing conventional metalfilms, such as tungsten, as the gap-fill material for (bWL) trenchstructures. The presence of line bending during device fabrication mayresult in undesirable device non-uniformity and a reduction in deviceyield. Replacing conventional gap-fill deposition processes andmaterials with the deposition processes and nucleationfilms/polycrystalline molybdenum films of the current disclosure mayallow for the reduction, or even elimination, of line bending duringdevice fabrication.

A non-limiting example of an application of the current disclosure isillustrated with reference to FIGS. 5A-C. FIG. 5A illustrates asubstrate including a number of vertical non-planar features prior to agap-fill metal formation, FIG. 5B illustrates the previous structure ofFIG. 5A following the deposition of a nucleation film directly on anexposed surface of the substrate, and FIG. 5C illustrates the previousstructure of FIG. 5B following the deposition of a polycrystallinemolybdenum film directly on the nucleation film.

In more detail, the structure 500 illustrated in FIG. 5A may include asubstrate 502 comprising a plurality of non-planar features andparticularly a plurality of vertical non-planar features 504. Forexample, the plurality of vertical non-planar features 504 may comprisea number of v-shaped vertical trenches disposed in the substrate 502. Insome embodiments, the vertical non-planar features may comprise highaspect ratio features which may have may have an aspect ratio(height:width) which may be greater than 2:1, or greater than 5:1, orgreater than 10:1, or greater than 25:1, or greater than 50:1, or evengreater than 100:1. In the example illustrated in FIG. 5A, the width ofthe v-shaped vertical trenches may be determined by measurement of thedistance between the uppermost extent of the opposing sidewalls of eachv-shaped vertical trench.

In additional applications, the substrate 500 may comprise a pluralityof alternative vertical non-planar features as described previouslyherein, or a combination of varieties of vertical non-planar featuresand/or horizontal non-planar features.

As illustrated in FIG. 5A, disposed between adjacent vertical non-planarfeatures 504 are a plurality of line features 506, such as, for example,protruding semiconductor or dielectric lines, or protrudingsemiconductor Fin structures.

In some embodiments of the disclosure, the plurality of line features506 may be formed as a regular array. For example, the line features 506may be arranged such that the pitch (x) between adjacent line features500 is substantially uniform, wherein the pitch (x) may be defined asthe distance between the middle vertical axis of one line feature (e.g.,axis 508A) to the middle vertical axis of an adjacent line feature(e.g., axis 508B).

In addition, the plurality of vertical non-planar features 504 may havesubstantially uniform profiles and dimensions. For example, the verticalnon-planar features 504 as illustrated in FIG. 5A comprise v-shapedvertical trenches with sloped sidewalls, wherein the width of thev-shaped vertical trenches decreases from the opening of the trench downto the base of the trench. As a non-limiting example, the plurality ofvertical non-planar features may comprise a substantially uniform width(y), wherein the width of each of the array of vertical non-planarfeatures may be determined by measurement of the distance across eachopening of the vertical non-planar features, i.e., a measurement of thedistance between the uppermost extent of the opposing sidewalls of avertical non-planar features.

As a non-limiting example, the structure 500 of FIG. 5A may correspondto a portion of a partially fabricated DRAM device structure prior to ametal gap-fill deposition, wherein the plurality of vertical non-planarfeatures 504 may comprise DRAM buried wordline trenches, and theplurality of line features 506 may comprise DRAM wordlines.

FIG. 5B illustrates a structure 510 which comprises the previousstructure 500 (of FIG. 5A) following the deposition of a nucleation film512 directly on an exposed surface of the substrate 502. The nucleationfilm 512 may be deposited by employing the deposition processes asdescribed herein (e.g., the first cyclical deposition process 220 ofFIG. 3) and the nucleation film 512 may have all the properties(materials, thicknesses, crystallinity, etc,) as previously describedherein. As illustrated in FIG. 5B, the nucleation film 512 may comprisea physically continuous film, however it should be noted that inalternative embodiments the nucleation film 512 may comprise aphysically discontinuous film (not illustrated).

As a non-limiting example, the exemplary structure 510 of FIG. 5B maycorrespond to a portion of a partially fabricated DRAM device structurepost deposition of a nucleation film directly on the DRAM buriedwordline trenches and DRAM wordlines.

FIG. 5C illustrates a structure 514 which comprises the previousstructure 510 (of FIG. 5B) following the deposition of a polycrystallinemolybdenum film 516 directly on the nucleation film 512. The polysiliconmolybdenum film 516 may be deposited by employing the depositionprocesses as described herein (e.g., the second cyclical depositionprocess 230 of FIG. 4) and the polysilicon molybdenum film 516 may haveall the properties (electrical resistivity, thickness, crystallinity,etc,) as previously described herein. As illustrated in FIG. 5C, thepolycrystalline molybdenum film 516 fills the entirety of the non-planarfeatures 504, e.g., from the base of a vertical trench to at least theuppermost extent (or opening) of a vertical trench. In addition, asillustrated in FIG. 5C the polycrystalline molybdenum film 516 disposedwithin and filling the plurality of non-planar features 504 is depositedwithout the without the formation of a seam.

In addition, FIG. 5C illustrates that the plurality of line features 506disposed between adjacent filled non-planar structures 504 have areduced line bending (or distortion), or are even free of line bending,following the deposition of the polycrystalline molybdenum film 516(i.e., compare the prior art structure 110 of FIG. 1B). The reduction orelimination of line bending in the plurality of line features 506 may beevident by the uniformity of the width of each of the verticalnon-planar features 504 following the metal gap-fill process. As anon-limiting example, the metal filled plurality of vertical non-planarfeatures 504 may comprise a width (z), wherein the width (z) of each ofthe metal filled array of vertical non-planar features may be determinedby measurement of the distance across the uppermost extent of the metalfilled vertical non-planar features.

In some embodiments, the reduction or elimination of line bendingresulting from the deposition processes and materials of the currentdisclosure, may be quantified by determining the percentage linebending.

As used herein, the term “percentage line bending” may refer to thedegree of line bending caused by the deposition of a gap-fill film on asubstrate including a regular array of non-planar features. Thepercentage line bending may be calculated by the following equation (I):

$\begin{matrix}{{{percentage}\mspace{14mu} (\%)\mspace{14mu} {line}\mspace{14mu} {bending}} = {( \frac{offset}{pitch} ) \times 100}} & (I)\end{matrix}$

wherein the offset is calculated by the following equation (II):

offset=|

z

−

y

|  (II)

or in other words, the value of the offset equals the absolute value ofthe average width of the non-planar features post gap-fill filmdeposition (average value of (z) of FIG. 5C), minus the average width ofthe non-planar features pre gap-fill film deposition (average value (y)of FIG. 5A). As a non-limiting example, the offset may be statisticallyestablished by measuring the width (y) of a plurality of non-planarfeatures prior to gap-fill film deposition and subsequently measuringthe width (z) for a plurality of non-planar features following thedeposition of a gap-fill film in the non-planar features

Therefore, in some embodiments, the percentage line bending of aplurality of line features 506 following the formation of apolycrystalline molybdenum film 516 directly on a plurality ofnon-planar features 504 disposed between adjacent line features may beless than 20%, or less than 10%, or less than 5%, or less than 2%, orless than 1%.

As a non-limiting example, a substrate may comprise a plurality ofvertical non-planar features and a plurality of line features. In suchan example, the nucleation film may comprise a molybdenum nitridenucleation film deposited directly on the plurality of verticalnon-planar features and the plurality of line features. After thedeposition of the molybdenum nitride nucleation film, a polycrystallinemolybdenum film may be deposited directly on the molybdenum nitridenucleation film, thereby filling the plurality of vertical non-planarfeatures (e.g., v-shaped vertical trenches, or tapered verticaltrenches) with the polycrystalline molybdenum film. In such an example,the percentage line bending of the plurality of line features may beless than 20%, or less than 10%, or less than 5%, or less than 2%, oreven less than 1%. In addition, the polycrystalline molybdenum film maycomprise a plurality of molybdenum crystallites having an averagecrystallite size of less than 90 Å, or less than 80 Å, or less than 70Å, or less than 60 Å, or even less than 50 Å. In this non-limitingexample, the molybdenum nitride nucleation film may have an average filmthickness of approximately 20 Å, the polycrystalline molybdenum film mayhave an average film thickness of approximately 100 Å and a percentsurface roughness of less than 5%.

In some embodiments, the line bending resulting from the deposition of agap-fill metal, e.g., a polycrystalline molybdenum film, may be reducedor even eliminated by performing a pre-treatment process on an exposedsurface of the substrate prior to the deposition of a nucleation layer.In some embodiments, the pre-treatment process may comprise contactingan exposed surface of the substrate, including non-planar features, witha pre-treatment gas. In some embodiments, the pre-treatment gas maycomprise an aluminum component, such as, for example, one or more of:trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminumhydride(DMAH), tritertbutylaluminum (TTBA), aluminum trichloride (AlCl₃), ordimethylaluminumisopropoxide (DMAI). In some embodiments, thepre-treatment gas may comprise a silicon component, such as, a silanegas. In some embodiments, a silane pre-treatment gas may comprise one ormore of: silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), tetrasilane(Si₄H₁₀), higher order silanes with the general empirical formulaSi_(x)H_((2x+2)), or even a chlorosilane, such as, dichlorosilane (DCS).In addition embodiments, the pre-treatment gas may comprise, water vapor(H₂O), or ammonia (NH₃).

In some embodiments of the disclosure, the pre-treatment process may beperformed on one or more of a dielectric surface, a semiconductorsurface, or a metallic surface. In particular embodiments, thepre-treatment process may be performed on a non-planar substratecomprising a dielectric surface.

In some embodiments, the pre-treatment process comprising contacting anon-planar substrate with a pre-treatment gas may be employed inaddition to the deposition of a nucleation film prior to polycrystallinemolybdenum film deposition. For example, a polycrystalline molybdenumfilm formation process may comprise: contacting an exposed surface of anon-planar substrate with a pre-treatment gas, subsequently depositing anucleation film directly on the pre-treated surface of the non-planarsubstrate, and then depositing a polycrystalline molybdenum filmdirectly on the nucleation film. In alternative embodiments, thepre-treatment process may be employed on an exposed surface of anon-planar substrate and the nucleation film deposition step may beomitted. For example, a polycrystalline molybdenum film formationprocess may comprise, contacting an exposed surface of a non-planarsubstrate with a pre-treatment gas, and subsequently depositing apolycrystalline molybdenum film directly on the pre-treated surface ofthe non-planar substrate.

Therefore, in some embodiments of the disclosure, the percentage linebending of a plurality of line features may be reduced or eveneliminated by contacting an exposed surface of a non-planar substratewith a pre-treatment gas either with or without the deposition of anintermediate nucleation film prior to deposition of a polycrystallinemolybdenum film. For example, in such embodiments employing apre-treatment of an exposed surface of a non-planar substrate thepercentage line bending of a plurality of pre-treated line features maybe less than 20%, or less than 10%, or less than 5%, or less than 2%, orless than 1%.

As a non-limiting example, the structure 514 of FIG. 5C may correspondto a portion of a partially fabricated DRAM device structure followingmetal gap-fill deposition, wherein the plurality of vertical non-planarfeatures 504 comprise DRAM buried wordline trenches, wherein the DRAMburied word line trenches are filled with the polycrystalline molybdenumfilm 516. In addition, the line features 506 may comprise the DRAMwordlines and in this non-limiting example the percentage line bendingof the plurality DRAM wordlines may be less than 20%, or less than 10%,or less than 5%, or less than 2%, or less than 1%.

The embodiments of the disclosure may also provide structures includinga polycrystalline molybdenum film formed according to the methodsdescribed herein. For example, the embodiments of the disclose mayprovide structures, such as, for example, semiconductor devicestructures, including partially fabricated semiconductor devicestructures, which include a polycrystalline molybdenum film formedaccording to the embodiments of the current disclosure. The structuresprovided herein may comprise: a substrate, a nucleation film disposeddirectly on a surface of the substrate, and a polycrystalline molybdenumfilm disposed directly on the nucleation film. The structures of thecurrent disclosure may be illustrated with reference to structure 514 ofFIG. 5C.

In more detail, the structure 514 of FIG. 5C may comprise: a surface ofa substrate; a nucleation film disposed directly on the surface of thesubstrate, wherein the nucleation film comprises at least one of a metaloxide nucleation film or a metal nitride nucleation film; and apolycrystalline molybdenum film disposed directly on the nucleationfilm; wherein the polycrystalline molybdenum film comprises a pluralityof molybdenum crystallites having an average crystallite size of lessthan 80 Å.

In more detail, in some embodiments the substrate 502 of structure 514(FIG. 5C) may comprise at least one of a dielectric material, a metallicmaterial, and a semiconductor material. The substrate 502 may compriseone or more of the previously disclosed substrate materials. Inaddition, the surface 518 of the substrate 502 may comprise at least oneof a dielectric surface, a metallic surface, or a semiconductor surface.The surface 518 of substrate 502 may comprise one or more of thepreviously described substrate materials and surfaces.

Further, the surface 518 of the substrate 502 may comprise a pluralityof non-planar features, such as, for example, vertical non-planarfeatures, and/or horizontal non-planar features. For example, substrate502 (FIG. 5C) includes the surface 518 including a plurality of verticalnon-planar features 504 (illustrated in FIG. 5C as v-shaped verticaltrenches). It should be appreciated that the surface 518 as describedherein may include one or more, or combination, of the previouslydisclosed non-planar features with the associated dimensions, profiles,aspect ratios, etc. In additional embodiments, the substrate 502 and theassociated surface 518 may further comprise a plurality of line features506, wherein each of the plurality of line features 506 may be disposedbetween adjacent non-planar features 504.

In some embodiments of the disclosure, the structure 514 (FIG. 5C) mayalso comprise a nucleation film 512 which may be disposed directly onthe surface 518 of the substrate 502. In some embodiments, thenucleation film 512 may comprise at least one of a metal oxidenucleation film or a metal nitride nucleation film.

In embodiments wherein the nucleation film 512 comprises a metal oxidenucleation film, the metal oxide nucleation film may comprise at leastone of: an aluminum oxide nucleation film, a molybdenum oxide nucleationfilm, a tungsten oxide nucleation film, a ruthenium oxide nucleationfilm, a rhenium oxide nucleation film, or an iridium oxide nucleationfilm. A metal oxide nucleation film of the current disclosure maycomprise a physically continuous nucleation film (as illustrated bynucleation film 512 of FIG. 5C) or a physically discontinuous nucleationfilm (not illustrated). In embodiments wherein the metal oxidenucleation film is physically continuous, the metal oxide nucleationfilm may be physically continuous at an average film thickness of lessthan 40 Å. In addition, a metal oxide nucleation film may have anaverage film thickness as previously disclosed herein, and in particularembodiments, a metal oxide nucleation film may have an average filmthickness of less than 30 Å. In some embodiments, a metal oxidenucleation film may comprise an amorphous metal oxide nucleation film.

In embodiments wherein the nucleation film 512 comprises a metal nitridenucleation film, the metal nitride nucleation film may comprise amolybdenum nitride nucleation film. A metal nitride nucleation film ofthe current disclosure may comprise a physically continuous nucleationfilm (as illustrated by nucleation film 512 of FIG. 5C) or a physicallydiscontinuous nucleation film (not illustrated). For example, amolybdenum nitride nucleation film may be physically continuous at anaverage film thickness of less than 40 Å. In addition, a metal nitridenucleation film may have an average film thickness as previouslydisclosed herein, and in particular embodiments, a metal nitridenucleation film may have an average film thickness of less than 30 Å. Insome embodiments, a metal nitride nucleation film may comprise a metalnitride nucleation film.

In some embodiments of the disclosure, the structure 514 (FIG. 5C) mayalso comprise a polycrystalline molybdenum film 516 which may bedisposed directly on the surface of the nucleation film 512.

In some embodiments, the polycrystalline molybdenum film 516 may bedisposed within a plurality of non-planar features 504 of the substrate502, wherein the polycrystalline molybdenum film 516 fills the pluralityof non-planar features 504 without any observable seam. For example, thesubstrate 502 may include a surface 518 comprising a plurality ofvertical non-planar features 504 (e.g., illustrated as vertical v-shapedtrenches in FIG. 5C). In some embodiments, the polycrystallinemolybdenum film 516 disposed within the plurality of non-planar features504 may be examined for the presence of an observable seam by a highmagnification microscopy technique, such as, for example, transmissionelectron microscopy (TEM), scanning electron microscopy (SEM), orscanning tunneling electron microscopy (STEM). If such highmagnification microscopy techniques do not reveal the presence of a seamthen it understood that the polycrystalline molybdenum film 516 disposedwithin the plurality of non-planar features 504 is seamless, i.e.,seam-free.

In additional embodiments of the disclosure, the surface 518 of thesubstrate 502 further comprises a plurality of vertical non-planarfeatures 504 and the nucleation film 512 is disposed directly on theplurality of vertical non-planar features 504. Further, thepolycrystalline molybdenum film 516 may be disposed directly on thenucleation film 512, wherein the polycrystalline molybdenum film 516fills the plurality of vertical non-planar features 504 without anyobservable seam, as determined utilizing high magnification microscopytechniques, as previously described herein.

In some embodiments, the structure 514 and particular the surface 518 ofthe substrate 502 may further comprise a plurality of line features 506.For example, each line feature 506 may be disposed between adjacentvertical non-planar features 504, such as, for example, between adjacentv-shaped vertical trenches as illustrated in FIG. 5C. In someembodiments, the plurality of line features 506 may be enclosed with anucleation film 512 disposed directly on the plurality of line features506. In addition, a polycrystalline molybdenum film 516 may disposeddirectly the nucleation film 512 enclosing the plurality of linefeatures 506. In some embodiments, the plurality of line features 506 ofstructure 514 may have a percentage line bending of less than 20%, orless than 10%, or less than 5%, or less than 2%, or less than 1%. Inparticular embodiments, the plurality of line features 506 of structure514 may have a percentage line bending of less than 20%. In furtherembodiments, the plurality of line features 506 of structure 514 mayhave a percentage line bending of less than 10%. In some embodiments,the plurality of line features 506 of structure 514 may have apercentage line bending between approximately 1% and 20%. In someembodiments, the plurality of line features 506 of structure 514 may besubstantially free of line bending, i.e., having a percent line bendingof approximately 0%.

In some embodiments, the polycrystalline molybdenum film 516 ofstructure 514 may have a surface roughness expressed as a percentageroughness of the total average film thickness of the polycrystallinemolybdenum film 516. For example, in some embodiments the percentagesurface roughness of the polycrystalline molybdenum film 516 may be lessthan 10%, or less than 5%, or less 3%, or less than 1.5%, or even lessthan 1%. In some embodiments, the percentage surface roughness of thepolycrystalline molybdenum film 516 may be between approximately 1% and10%.

In some embodiments, the polycrystalline molybdenum film 516 ofstructure 514 may comprise a plurality of molybdenum crystalliteswherein the average crystallite size may be less than 100 Å, or less 80Å, or less than 60 Å, or less than 40 Å, or even less than 20 Å. In someembodiments, the molybdenum crystallites may have an average crystallitesize between approximately 20 Å and 100 Å, or between approximately 20 Åand 75 Å, or even between approximately 20 Å and 50 Å.

As a non-limiting example, the polycrystalline molybdenum film 516 maybe deposited directly on a molybdenum nitride nucleation film and themolybdenum crystallites of the polycrystalline molybdenum film 516 mayhave an average crystallite size of less than approximately 60 Å, orless than approximately 50 Å, or even less than approximately 40 Å, orbetween approximately 20 Å and 60 Å. In a particular example, thenucleation film 512 may comprise a molybdenum nitride nucleation filmand the polycrystalline molybdenum film 516 has an average crystallitesize of less than 60 Å and has a percentage roughness of less than 10%.

In some embodiments, the nucleation film 512 and the polycrystallinemolybdenum film 516 together constitute a bilayer disposed directly onthe surface 518 of the substrate 502. In some embodiments, the bilayermay have an electrical resistivity of less than 50 μΩ-cm, or less than30 μΩ-cm, or less than 20 μΩ-cm, or even less than 25 μΩ-cm, or betweenapproximately 25 μΩ-cm and 50 μΩ-cm, wherein the bilayer may comprise anucleation film with an average film thickness of less than 20 Å and apolycrystalline molybdenum film with an average film thickness of than100 Å.

In some embodiments of the disclosure, the structure 514 (FIG. 5C) maycomprise a device structure, and in some embodiments, a partiallyfabricated device structure. For example, a partially fabricated devicestructure may comprise at least one of a DRAM device structure, a3D-NAND device structure, a 3D-integrated device structure, or anintegrated logic device structure.

In embodiments wherein the structure 514 comprises a partiallyfabricated DRAM device structure, the non-planar substrate 502 maycomprise a plurality of non-planar features 504 comprising a pluralityof DRAM buried wordline trenches, in addition the plurality of linefeatures 506 may comprise a plurality of DRAM wordlines. In suchembodiments, the nucleation film 512 may be disposed directly on theplurality of DRAM buried wordline trenches and directly on the pluralityof DRAM wordlines.

In embodiments wherein structure 514 comprises a partially fabricatedDRAM device structure, the polycrystalline molybdenum film 516 may bedisposed within and fills the plurality of DRAM buried wordlinetrenches. In such embodiments, the polycrystalline molybdenum film 516disposed within and filling the plurality of DRAM buried wordlinetrenches may comprise no observable seams, i.e., the filled DRAM buriedwordline trenches are seamless, as determined by high magnificationmicroscopy techniques as previously described herein.

In addition, in embodiments wherein the structure 514 comprises apartially fabricated DRAM device structure, the percentage line bendingof the plurality of DRAM wordlines, may be less than 20%, or less than10%, or less than 5%, or less than 2%, or less than 1%, or even betweenapproximately 1% and 20%. In some embodiments, the plurality DRAMwordlines may be substantially free of line bending, i.e., having apercent line bending of approximately 0%.

As a non-limiting example, the structure 514 may comprise a partiallyfabricated DRAM device structure including a polycrystalline molybdenumfilm 516 disposed directly on an molybdenum nitride nucleation film 512.In such a partially fabricated DRAM device structure, the plurality ofmolybdenum crystallites of the polycrystalline molybdenum film 516 mayhave an average crystallite size of less than approximately 60 Å, orless than approximately 50 Å, or even less than approximately 40 Å, orbetween approximately 40 Å and 60 Å. As a particular example of apartially fabricated DRAM device structure, the nucleation film 512 maycomprise a molybdenum nitride nucleation film and the polycrystallinemolybdenum film 516 may have an average crystallite size of less than 60Å and a percentage roughness of the polycrystalline molybdenum film 516of less than 10%.

The example embodiments of the disclosure described above do not limitthe scope of the invention, since these embodiments are merely examplesof the embodiments of the invention, which is defined by the appendedclaims and their legal equivalents. Any equivalent embodiments areintended to be within the scope of this invention. Indeed, variousmodifications of the disclosure, in addition to those shown anddescribed herein, such as alternative useful combination of the elementsdescribed, may become apparent to those skilled in the art from thedescription. Such modifications and embodiments are also intended tofall within the scope of the appended claims.

What is claimed is:
 1. A method for forming a polycrystalline molybdenumfilm over a surface of a substrate, the method comprising: providing asubstrate into a reaction chamber; depositing a nucleation film directlyon an exposed surface of the substrate, wherein the nucleation filmcomprises one of a metal oxide nucleation film or a metal nitridenucleation film; and depositing a polycrystalline molybdenum filmdirectly on the nucleation film; wherein the polycrystalline molybdenumfilm comprises a plurality of molybdenum crystallites having an averagecrystallite size of less than 80 Angstroms.
 2. The method of claim 1,wherein depositing the nucleation film comprises performing one or morefirst unit deposition cycles of a first cyclical deposition process,wherein a first unit deposition cycle comprises, sequentially contactingthe substrate with a metal precursor and with one of an oxygenprecursor, or a nitrogen precursor.
 3. The method of claim 1, whereindepositing the polycrystalline molybdenum metal film comprisesperforming one or more second unit deposition cycles of a secondcyclical deposition process, wherein a second unit deposition cyclecomprises, sequentially contacting the substrate with a molybdenumhalide precursor and a reducing agent.
 4. The method of claim 3, whereinthe molybdenum halide precursor comprises at least one of: molybdenum(V) trichloride oxide (MoOCl₃), molybdenum (VI) tetrachloride oxide(MoOCl₄), or molybdenum (IV) dichloride dioxide (MoO₂Cl₂).
 5. The methodof claim 1, wherein the metal oxide nucleation film comprises at leastone of: an aluminum oxide nucleation film, a molybdenum oxide nucleationfilm, a tungsten oxide nucleation film, a ruthenium oxide nucleationfilm, a rhenium oxide nucleation film, or an iridium oxide nucleationfilm, and the metal oxide nucleation film has an average film thicknessof less than 50 Å.
 6. The method of claim 1, wherein the metal nitridenucleation film comprises a molybdenum nitride nucleation film, and themolybdenum nitride nucleation film has an average film thickness of lessthan 30 Å.
 7. The method of claim 1, wherein the polycrystallinemolybdenum film is deposited within a plurality of non-planar features,wherein the polycrystalline molybdenum film fills the plurality ofnon-planar features without the formation of a seam.
 8. The method ofclaim 1, wherein a bilayer comprising the polycrystalline molybdenumfilm and the nucleation film has an electrical resistivity of less 25μΩ-cm for an average nucleation film thickness of less than 20 Å, and anaverage polycrystalline molybdenum film thickness of less than 100 Å. 9.The method of claim 1, wherein the nucleation film is a physicallycontinuous film at an average film thickness of less than 50 Å.
 10. Themethod of claim 1, wherein the exposed surface of the substrate includesa plurality of vertical non-planar features and the nucleation film isdeposited directly on the exposed surface, and the polycrystallinemolybdenum film is deposited directly on the nucleation film, whereinthe polycrystalline molybdenum film fills the plurality of verticalnon-planar features without the formation of a seam.
 11. The method ofclaim 10, wherein the exposed surface comprises a dielectric surface.12. The method of claim 10, wherein the substrate further comprises aplurality of line features, wherein the percentage line bending of theplurality of line features is less than 20% post deposition of thenucleation film and the polycrystalline molybdenum film.
 13. The methodof claim 10, wherein the substrate further comprises a plurality of linefeatures, wherein the percentage line bending of the plurality of linefeatures is less than 10% post deposition of the nucleation film and thepolycrystalline molybdenum film.
 14. The method of claim 10, wherein thenucleation film comprises a molybdenum nitride nucleation film.
 15. Themethod of claim 14, wherein the polycrystalline molybdenum film has anaverage crystallite size of less than 60 Å.
 16. The method of claim 1,wherein the polycrystalline molybdenum film has a percentage roughnessof less than 10%.
 17. The method of claim 1, wherein the polycrystallinemolybdenum film has a percentage roughness of less than 5%.
 18. Themethod of claim 1, wherein the nucleation film comprises a molybdenumnitride nucleation film and the polycrystalline molybdenum film has apercentage roughness of less than 10%.
 19. The method of claim 1,wherein the exposed surface of the substrate comprising a dielectricsurface.
 20. A structure comprising the polycrystalline molybdenum filmformed according to the method of claim
 1. 21. A reaction systemconfigured to perform the method of claim
 1. 22. A structure comprising:a surface of a substrate; a nucleation film disposed directly on thesurface of the substrate, wherein the nucleation film comprises at leastone of a metal oxide nucleation film or a metal nitride nucleation film;and a polycrystalline molybdenum film disposed directly on thenucleation film; wherein the polycrystalline molybdenum film comprises aplurality of molybdenum crystallites having an average crystallite sizeof less than 80 Å.
 23. The structure of claim 22, where the metal oxidenucleation film comprises at least one of: an aluminum oxide nucleationfilm, a molybdenum oxide nucleation film, a tungsten oxide nucleationfilm, a ruthenium oxide nucleation film, a rhenium oxide nucleationfilm, or an iridium oxide nucleation film, and the metal oxidenucleation film has an average film thickness of less than 50 Å.
 24. Thestructure of claim 22, wherein the metal nitride nucleation filmcomprises a molybdenum nitride nucleation film having an average filmthickness of less than 30 Å.
 25. The structure of claim 22, wherein thepolycrystalline molybdenum film is disposed within a plurality ofnon-planar features, wherein the polycrystalline molybdenum film fillsthe plurality of non-planar features without an observable seam.
 26. Thestructure of claim 22, wherein a bilayer comprising the polycrystallinemolybdenum film and the nucleation film has an electrical resistivity ofless than 25 μΩ-cm for an average nucleation film thickness of less than20 Å and an average polycrystalline molybdenum film thickness of lessthan 100 Å.
 27. The structure of claim 22, wherein the nucleation filmis a physically continuous film with an average film thickness of lessthan 40 Å.
 28. The structure of claim 22, wherein the surface of thesubstrate further comprises a plurality of vertical non-planar featuresand the nucleation film is disposed directly on the plurality ofvertical non-planar features and the polycrystalline molybdenum film isdisposed directly on the nucleation film, wherein the polycrystallinemolybdenum film fills the plurality of vertical non-planar featureswithout an observable seam.
 29. The structure of claim 22, wherein thesurface of the substrate comprises a dielectric surface.
 30. Thestructure of claim 28, wherein the substrate further comprises aplurality of line features, wherein the percentage line bending of theplurality of line features is less than 20%.
 31. The structure of claim28, wherein the substrate further comprises a plurality of linefeatures, wherein the percentage line bending of the plurality of linefeatures is less than 10%.
 32. The structure of claim 28, wherein thenucleation film comprises a molybdenum nitride nucleation film.
 33. Thestructure of claim 32, wherein the polycrystalline molybdenum film hasan average crystallite size of less than 60 Å.
 34. The structure ofclaim 22, wherein the polycrystalline molybdenum film has a percentageroughness of less than 10%.
 35. The structure of claim 22, wherein thesubstrate comprises a partially fabricated device structure including atleast one of: a DRAM device structure, a 3D-NAND device structure, a3D-integrated device structure, or an integrated logic device structure.36. The structure of claim 35, wherein the substrate comprises apartially fabricated DRAM device structure, wherein the substratecomprises a plurality of DRAM buried wordline trenches and a pluralityof DRAM wordlines.
 37. The structure of claim 36, wherein the nucleationfilm is disposed directly on the plurality of DRAM buried wordlinetrenches and directly on the plurality of DRAM wordlines.
 38. Thestructure of claim 37, wherein the polycrystalline molybdenum film isdisposed within and fills the plurality of DRAM buried word linetrenches.
 39. The structure of claim 38, wherein the percentage linebending of the plurality of DRAM wordlines is less than 20%.
 40. Thestructure of claim 39, wherein the nucleation film comprises amolybdenum nitride nucleation film and the polycrystalline molybdenumfilm has a percentage roughness of than 1.5%.